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系統識別號 U0026-2002201117223300
論文名稱(中文) 運用分子模板於香菸中半揮發有機物檢測方法研發
論文名稱(英文) Development of Molecular Imprinting Polymers for Analysis of PAHs in Mainstream Cigarette Smoke
校院名稱 成功大學
系所名稱(中) 環境工程學系碩博士班
系所名稱(英) Department of Environmental Engineering
學年度 99
學期 2
出版年 100
研究生(中文) 何緯倫
研究生(英文) Wei-Lun Ho
學號 P5894108
學位類別 博士
語文別 中文
論文頁數 136頁
口試委員 指導教授-林達昌
口試委員-陳瑞仁
口試委員-李文智
口試委員-蔡朋枝
口試委員-趙木榮
中文關鍵字 分子模板  香菸  主流煙  多環芳香烴化合物  7-MeBP 
英文關鍵字 molecular imprinting polymers  PAHs  cigarette  main stream  7-MeBP 
學科別分類
中文摘要 本研究結合分子模板與固相萃取技術進行環境樣品前處理的方法研發,並評估其應用於實際環境空氣樣品的成效。運用熱聚合方式,進行不同交聯劑與官能基單體配比進行分子模板製備,總計製備 6 組分子模板進行研究,分子模板的製備以Benz[a]Pyrene(BaP)為目標分子,之後進行吸附量、選擇性、回收率、漏出測試、電子顯微鏡表面觀察、微差熱卡分析與比表面積測試等多種分子模板之材料特徵分析,再選擇其中具有較大吸附量、選擇性與回收率之分子模板進行實際環境樣品(以香菸燃燒之主流煙為對象)。
分子模板材料特徵測試部分,研究結果顯示不同配比條件的分子模板在材料特徵上有顯著差異,吸附量、選擇性、回收率、電子顯微鏡觀察、微差熱卡分析與比表面積測結果顯示,官能基單體對於分子模板的材料特徵有較大的影響,次之為交聯劑。分子模板對目標分子吸附量以官能基 4-VP配合交聯劑 EDMA具有較高的吸附量為 12.80 ± 1.3 μg/g;在混有 16 種 PAHs條件下進行選擇性測試,以官能基 TRIM配合交聯劑 MAA對BaP具有較高的選擇性;比表面積測試結果顯示以官能基 4-VP、MAA配合交聯劑 EDMA分子模板對材料的表面積(Surface area)、總孔隙體積(Total pore volume)、微孔隙比表面積(Micropore specific surface area)及微孔隙體積(Micropore volume)有顯著的差異。
實際環境樣品測試部分,以美國肯塔基大學農業學院所生產之標準測試香菸 3R4F為測試對象,採樣方法是根據美國聯邦交易委員會制定的規則進行,用劍橋石英濾紙採集主流煙之固相物,其後以索氏萃取方法進行萃取,研究結果顯示,香菸主流煙中經矽膠管柱淨化後 BaP的濃度為 11.5 ng/cig。
所有研究結果顯示,相較於傳統的萃取技術,MISPE可以更有效的吸附BaP,減少背景干擾增加訊號解析度,此外使用MISPE管柱於樣品前處理可以降低溶劑使用與時間消耗,再者MISPE可以從複雜的樣品中選擇性的萃取出有毒物質。結合MIP-4(MAA-co- TRIM)與SPE可以為環境樣品前處理提供一個很有效的工具去選擇性的分離致突變性PAHs,本研究也同時是第一個運用分子模板於香菸樣品中微量BaP分析的研究。
英文摘要 In this study benz[a]pyrene (BAP) was selected as the template molecule. Several different imprinted polymers were synthesized and studied for their characteristics and application efficiencies in environmental sampling. After preparation of the molecular imprinted polymer (MIP) and non-imprinted polymer (NIP), their capacities, selectivity, recovery, and breakthrough were determined by SEM analyses, differential scanning calorimeter (DSC), and the BET surface properties test. Results show that some MIPs have good selectivity toward benz[a]pyrene from among a mixture containing 16 PAHs.
Analytical results show that the combination of using 4-vinylpyridine (4-VP) as a functional monomer, along with dimethacrylate (EDMA) as the crosslinker resulted in a higher adsorption capacity 12.80 ± 1.3 μg/g than other MIPs. The SEM micrographs reveal that the surface characteristics of particles were related to the different crosslinkers. The DSC test indicates that both the functional monomer and crosslinker were important controlling factors of imprinted polymers and NIPs. In addition, the surface properties of imprinted polymers and NIPs demonstrate that MIP pore size was larger that that of NIP, implying that the pore size may affect the capacity and selectivity of MIP.
In this study, Kentucky reference cigarettes 3R4F were sampled. The benz[a]pyrene levels obtained by Soxhlet extraction was 11.5 ng/cig, respectively.
All the experimental results suggest that MISPE can more effectively adsorb BaP among the 16 different PAHs in mixtures, reduce background interferences and increase signal resolution as compared to traditional extraction techniques. Additionally, using MISPE cartridges in sample pretreatment reduces both the analysis time and the amount of organic solvents used. In addition, using MISPE may also extract toxic target analytes from a complex sample selectively, and more effectively than traditional Soxhlet extraction. The combination of MIP-4 and SPE for environmental sample pretreatment offers a useful tool for selective isolation of the mutagenic PAHs. This study is also the first to apply an MISPE cartridge in the analysis of trace level BaP in cigarette smoke.
論文目次 學位考試 II
中文摘要 III
英文摘要 V
誌 謝 VII
總目錄 X
表目錄 XIV
圖目錄 XVI
1-1 研究動機 1
1-2 研究目的與內容 2
第二章 文獻回顧 4
2-1 微量分析之概念與應用 4
2-1-1 微量分析與樣品前處理 4
2-1-2 固相萃取技術 6
2-1-3 固相萃取的未來發展 7
2-2 分子模板的介紹 7
2-2-1分子模板之簡介 7
2-2-2分子鎖與分子鑰匙 9
2-2-3分子模板合成技術 10
2-2-4分子模板的組成 11
2-2-5分子模板在環境上的運用 13
2-2-6固相萃取法與分子模板萃取法比較 16
2-3 PAHs 17
2-3-1 PAHs 的定義 17
2-3-2 PAHs 的形成機制 21
2-3-3 Bay-Region與PAHs之致癌機制 22
2-4 香菸的介紹 24
2-4-1香菸之組成與燃燒過程 24
2-4-2香菸中的主要危害物質 28
2-4-3香菸致癌機制 32
第三章 實驗方法與步驟 34
3-1研究方法 34
3-2實驗設計 36
3-2-1分子模板製備 36
3-2-1-1分子模板材料測試 40
3-2-1-2分子模板吸附量 40
3-2-1-3分子模板選擇性 40
3-2-1-4分子模板回收率 41
3-2-1-5洩漏測試 42
3-2-1-6微差掃描熱卡分析 43
3-2-1-7比表面積測試 43
3-2-1-8電子顯微鏡觀察 44
3-2-2 相似結構拓印分子製備 45
3-3採樣前之準備 46
3-3-1濾紙前處理 46
3-3-2分子模板前處理 46
3-4 採樣對象與設備 47
3-4-1香菸選擇 47
3-4-2採樣設計與規劃 48
3-4-3採樣設備 49
3-4-4採樣地點 49
3-5香菸主流煙採樣 49
3-5-1傳統濾紙採樣 50
3-5-2萃取方式 51
3-5-2-1索氏萃取 51
3-5-2-2超音波震盪萃取 51
3-5-3淨化程序 52
3-5-3-1矽膠管柱淨化 52
3-5-3-2 分子模板管柱淨化 54
3-6 PAHs分析 56
第四章 數據分析之品質保證及品質控制 57
4-1 空白試驗 57
4-1-1 溶劑空白試驗 57
4-1-2 程序空白試驗 57
4-2 標準品回收測試 58
4-3 PAHs化合物分析程序之QA/QC 61
第五章 結果與討論 67
5-1 分子模板材料測試 67
5-1-1 分子模板比吸附量 67
5-1-2 分子模板選擇性 70
5-1-3 分子模板回收率 74
5-1-4 洩漏測試 75
5-1-5 微差掃描熱卡分析 76
5-1-6比表面積測試 78
5-1-7電子顯微鏡觀察 81
5-1-8 小結 82
5-2 7-MeBP分子模板製備測試探討 82
5-2-1 吸附量 82
5-2-2 選擇性 83
5-2-3 回收率 84
5-2-4 小結 84
5-3香煙樣品採樣 87
5-3-1標準香菸採樣後之層析圖 87
5-4 標準香菸採樣後淨化 88
5-4-1矽膠管柱淨化後之層析圖 88
5-4-2 MIP管柱淨化後之層析圖 89
5-4-3不同淨化結果比較 96
5-4-4降低背景干擾之效果評估 99
第六章 結論與建議 106
6-1結論 106
6-2建議 108
參考文獻 109
附錄A 十六種PAHs之離子選擇 116
附錄B 十六種PAHs之檢量線(GC/MS) 117
自述 133
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